Investigation of the removal of Ni(II) from aqueous solution using pomelo fruit peel
|
Physical sciences Chemistry
DOI: 10.31276/VJSTE.63(2).07-12
Investigation of the removal of Ni(II)
from aqueous solution using pomelo fruit peel
Van phuc Dinh*
Duy Tan University
Received 8 September 2020; accepted 4 December 2020
Abstract:
Pomelo fruit peel, an organic waste, was utilised as a biosorbent to remove Ni(II) from aqueous solutions. Some
major factors influencing Ni(II) uptake such as pH, adsorption time, and initial Ni(II) concentration were examined.
Several isotherm and kinetic models including the Langmuir, Freundlich, Sips, pseudo-first-order, pseudo-second-
order, and intra-diffusion models were fit to the experimental data. Results showed that the Ni(II) uptake obtained
an equilibrium at pH=6 after 80 min at 303 K. The Sips isotherm model described the Ni(II) adsorption better than
other models and the monoadsorption capacity calculated from the Langmuir model was 9.67 mg/g. The adsorption
of Ni(II) followed pseudo-second-order kinetic models with three stages.
Keywords: biosorption, isotherm models, Ni(II), pomelo fruit peel.
Classification number: 2.2
peel [14], and Citrus reticulata (fruit peel of orange) [15].
However, the utilisation of pomelo fruit peel (Citrus grandis)
Introduction
In recent years, the expansion of many industries has
as a biosorbent to remove Ni(II) from aqueous solutions
promote a huge increase in the economy of a large number
has been limited. In previous reports, the pomelo fruit peel
of developing countries. However, the governments in these
countries are faced with significant environmental problems
especially those related to heavy toxic metal pollution in
the effluent of industrial zones. Ni(II) is one such heavy
toxic metal, which has existed in the wastewater of many
factories such as electroplating, mineral processing,
was used to adsorb methylene blue [16], Cr(III) [16], Pb(II)
[17], and Cd(II) [17]. The obtained results indicated that
the pomelo fruit peel is a potential biosorbent to uptake
heavy toxic metals and organic molecules from aqueous
solutions. Therefore, in this work, the study is extended to
Ni(II) adsorption onto the pomelo fruit peel. The pHsolution
,
batteries manufacturing, and so on [1, 2]. As claimed by
the World Health Organization (WHO), the limit of Ni(II)
concentration in water is 0.005 kg/m3 [2]. Hence, various
physicochemical methods have been applied to eliminate
Ni(II) from aqueous solutions including adsorption [1-4],
precipitation [5, 6], ion-exchange [7, 8] and so on. Among
them, adsorption is a promising method since it is simple,
low-cost, and easily reused [9, 10].
adsorption time, and initial Ni(II) concentration, all of which
affect the Ni(II) adsorption, are examined. Some common
isotherm and kinetic models are fit to the experimental data
to understand the nature of the uptake.
Materials and methods
Preparation of biosorbent
The biosorbent was prepared identical to the author’s
previous studies [17]. Herein, the pomelo fruit peel was
washed by deionised water several times after collection
from the Vinh Cuu district, Dong Nai province, Vietnam.
The material was then dried in an oven at 80oC within 24
h, prior to cutting into small pieces about 0.5-1 mm in size.
The use of agricultural waste as biosorbents has attracted
many scientists because they are abundantly available,
environmentally friendly, and low cost. There are many
biosorbents used to remove Ni(II) from aqueous solutions
including Sophora japonica pod powder [11], Sargassum
sp. [12], activated banana peel [13], modified plantain Finally, the biosorbent was stored in the oven.
*Email: dinhvanphuc@duytan.edu.vn
Vietnam Journal of Science,
June 2021 • Volume 63 number 2
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Chemicals
Table 1. Some common nonlinear isotherm and kinetic models.
The Ni (II) ion was used as an adsorbate, which was
prepared by dissolving a Ni(II) standard (1000 mg/l) in
deionised (DI) water. The pH adjustment of the investigated
solution was carried by using HNO3 and NaOH with
different concentrations. All experimental chemicals used
in this work were from Merck (Germany) and were in the
analytical reagent grade.
Models
Nonlinear forms
Nomenclature
Isotherm models
Qe (mg/g): amount of adsorbate in the
adsorbent at equilibrium.
Qm (mg/g): maximum monolayer
adsorption capacity.
KL (l/mg): Langmuir isotherm constant.
KF [(mg/g).(l/mg)1/n]: Freundlich isotherm
constant.
Qm.KL.Ce
Qe =
Langmuir
Freundlich
1+ KL.Ce
Qe = KF .Ce1/n
Qs.Ceb
s
Instruments
n: heterogeneity factor.
Qe =
Sips
1+as.Ceb
s
Qs (l/g): Sips isotherm model constant.
αs (l/mg): Sips isotherm model constant.
βs: Sips isotherm model exponent.
The pH meter (Martini instruments, Mi-15, Romania),
with buffer solution values of 4.01±0.01, 7.01±0.01, and
10.01±0.01, was used to determine the pHsolution values.
The material’s morphology was examined by ultrahigh
resolution SEM (S-4800), whereas the bonding in the
materials’ structure was found out by Fourier-transform
infrared (FT-IR) spectroscopy that was conducted on a
Tensor 27 (Bruker, Germany).
Kinetic models
Pseudo-first-
order
Q = Qe 1− e−k t
1
Qt (mg/g): adsorption capacity at time t.
Qe (mg/g): adsorption capacity at the
equilibrium.
t
Qe2.k2.t
Pseudo-second-
order
k1 (min-1): pseudo-first-order model
constant.
Q =
t
1+ k2.Qe.t
k2 (g.mg-1.min-1): pseudo-second-order
model constant.
Q = kdt1/2 + C
Intra-diffusion
t
kd: intra-diffusion models constant.
In order to determine the Ni(II) concentration before and
after the uptake, an atomic absorption spectrophotometer
(Shimadzu AA-7000, Japan) was used.
Results and discussion
Characterisations of the biosorbent
Batch adsorption study
SEM - EDX analyses: Figs. 1Aand 1B show SEM images
of pomelo fruit peel at 1.00k and 10.0k magnifications. As
seen in these images, the adsorbent surface is very rough,
porous, and heterogeneous. These properties are favourable
for the heavy metal ion adsorption. The elemental
composition of this material was determined by energy-
dispersive X-ray spectroscopy (EDX), which is presented
in Fig. 1C. The results confirm that the weight percentages
of carbon and oxygen were 47.41 and 52.59%, respectively.
The Ni(II) batch adsorption onto the pomelo fruit peel
was carried on IKA magnetic stirrers with a RT 10 P heater.
Herein, 0.1 g of the synthesised material was placed into
100 ml flasks together with 50 ml of Ni(II) aqueous solution.
These flasks were stirred at a constant rate of 150 rpm. The
factors affecting the uptake including pH (2-6), adsorption
time (10-240 min), and Ni(II) initial concentration (5-50
mg/l) were examined.
The percentage of the Ni(II) uptake (% removal) and
adsorption capacity, Qe, (mg/g) were determined based on
the following equations:
Point of zero charge (pHPZC): pHPZC is the pH value of
the solution when the material’s surface charge is neutral.
Indeed, if pHsolution is less than pHPZC, the material surface is
positively charged. In contrast, the material’s surface charge
is negative when pHsolution>pHPZC. Fig. 1D presents the pHPZC
of the pomelo fruit peel in this study, which was determined
to be 4.6.
(Co -Ce )
(1)
% Removal =
.100%
Co
(Co -Ce ).V
(2)
Qe =
m
FT-IR spectrum: Fig. 2 depicts the vibrations of
characteristic groups in the pomelo fruit peel. As seen in this
figure, the vibrations of the O-H groups of pectin, cellulose,
and lignin are recorded at 3246 cm-1, while the vibrations of
the C-H bonds in the CH2 and CH3 groups are assigned to
wavenumbers 2924 cm-1 and 2851 cm-1, respectively. The
wavenumbers 1747 cm-1 and 1643 cm-1 are related to the
C=O groups [19]. Finally, the wavenumbers 1107 cm-1 and
1026 cm-1 confirm the C-O group’s stretching vibrations in
the lignin structure of pomelo fruit peel [16].
where the Ni(II) concentration in the aqueous solution
before and after the adsorption are symbolised Co (mg/l) and
Ce (mg/l), respectively, V is the volume (l) of metal solution,
and m is the mass (g) of the material used.
Adsorption isotherm and kinetic models
In this report, some common adsorption isotherm and
kinetic models are fit to the experimental data [17, 18].
These models are given in Table 1.
Vietnam Journal of Science,
June 2021 • Volume 63 number 2
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Physical sciences Chemistry
Fig. 1. (A, B) SEM images at different magnifications, (C) the EDX spectrum, and (D) pHPZC of the pomelo fruit peel.
that the uptake of Ni(II) rises rapidly when pHsolution is
increased from 2 to 4. In the next stage, there is a slight
increase in the adsorption prior to obtaining the maximum
at pH=6. The increase in pHsolution from 2 to 6 leads to a
change in material surface charge from positive to negative.
At pHsolution>pHPZC=4.6, the material’s surface charge is
negative, which leads to a rise in Ni(II) adsorption due to
the electrostatic attraction between Ni(II) cations and the
negatively-charged material surface [20, 21]. However, the
author observed that nickel (II) hydroxide can be formed
at pHsolution>6. Therefore, pH=6 is chosen for further
experiments.
Fig. 2. FT-IR spectrum of pomelo fruit peel.
The adsorption time: the influence of the adsorption
time on the Ni(II) biosorption by pomelo fruit peel is
indicated in Fig. 3B. The uptake rate of Ni(II) significantly
increases prior to reaching equilibrium at 80 min and then
remained stable. Therefore, the optimal adsorption time was
determined to be 80 min.
Factors affecting the removal of Ni(II)
pHsolution: pHsolution directly affects the removal of Ni(II)
due to its effects on the formation of different complexes of
Ni(II) and the surface charge of materials. Fig. 3A indicates
Vietnam Journal of Science,
June 2021 • Volume 63 number 2
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Physical sciences Chemistry
Fig. 3. Plots of the effects of (A) pHsolution and (B) adsorption time on Ni(II) adsorption.
Fig. 4. Plots of (A) isotherm models and (B) kinetic models of the Ni(II) adsorption onto pomelo fruit peel.
Isotherm studies
Table 2. Parameters of nonlinear isotherm models at temperature
of 303 K.
The plots of several common isotherm models including
Langmuir, Freundlich, and the Sips models are presented in
Fig. 4A. The nonlinear isotherm parameters of these models
are listed in Table 2. According to calculated RMSE and
χ2 values, the experimental data had a better fit with the
Sips model than the others as determined by the smallest
RMSE and χ2 values. The main reason is that the Langmuir
and Freundlich models are constrained by the adsorbates’
concentration, while the Sips model combines these
models and overcomes this problem [18]. Furthermore, the
Langmuir maximum monolayer adsorption capacity was
9.67 mg/g, which is higher than other biosorbents such as
hazelnut shell, fly ash, rice husk, banana peel, and doum
palm (Hyphaene thebaica L.) (Table 3). The n value (n=2.67)
evaluated from the Freundlich model ranges from 1 to 10
and indicates how favourable conditions are for adsorption
[18, 22]. However, the Ni(II) adsorption capacity is lower
than Pb(II), Cd(II), and Cr(III) when the same pomelo fruit
peel is used [16, 17]. This shows that the pomelo fruit peel
is a potential material for removing heavy metals from
aqueous solutions.
Isotherm models
parameters
KL (l/mg)
0.1891
9.67
Qm (mg/g)
Langmuir
RMSE
0.2625
0.9854
0.1413
2.67
R2
c2
n
KF [(mg/g).(l/mg)1/n
]
2.48
Freundlich
RMSE
R2
0.3752
0.9701
0.2519
2.25
c2
Qs (l/g)
as (l/mg)
bs
0.1938
0.7667
0.1975
0.9917
0.0428
Sips
RMSE
R2
c2
Vietnam Journal of Science,
June 2021 • Volume 63 number 2
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Physical sciences Chemistry
Table 3. Maximum adsorption capacities of several biosorbents intra-diffusion model is therefore applied to determine the
for the Ni(II) uptake from aqueous solutions [23-27].
Ni(II) adsorption kinetic onto pomelo fruit peel. As seen
from the plot of Qe versus t1/2 in Fig. 4B, the removal of
Ni(II) includes three stages. Firstly, Ni(II) cations are steeply
transferred from the solution to the material’s surface within
about 20 min. In the next stage, the Ni(II) uptake more
gradually occurs from 20 to 80 min, prior to obtaining the
equilibrium in the last stage. From the nonzero C value
calculated from the intra-diffusion model, the Ni(II) uptake
follows not only the intra-diffusion process but also two or
more different mechanisms [28, 29].
Adsorptive
condition
Adsorption
capacity (mg/g)
Biosorbents
References
Doum palm (Hyphaene
thebaica L.)
pH=7.00, t=120 min 3.24
[1]
Banana peel
Rice husk
pH=6.89, t=24 h
pH=6.00, t=120 min 8.86
pH=8.00, t=60 min 0.03
pH=7.00, t=180 min 7.18
6.88
[23]
[24]
[25]
[26]
Fly ash
Hazelnut shell
Cone biomass of Thuja
orientalis
Conclusions
pH=4.00, t=7 min
12.42
[27]
The Ni(II) adsorption onto pomelo fruit peel was
investigated. The results showed that the Ni(II) uptake
reached equilibrium at pH=6.00 after 80 min at 303 K.
Kinetic studies showed that the Ni(II) uptake was controlled
byvariousmechanisms.TheLangmuirmaximumadsorption
capacity was 9.67 mg/g, which was higher than some other
biosorbents. Therefore, pomelo fruit peel can be used as a
promising, eco-friendly, and low-cost material to eliminate
Ni(II) from the effluent.
Brown algae
Sargassum sp.
pH=6.00, t=90 min
pH=6.00, t=80 min
50.97
9.67
[12]
Pomelo fruit peel
This study
Kinetic studies
Figure 4B and Table 4 present the plots of the kinetic
models and non-linear parameters, respectively. Clearly, the
pseudo-second-model fit to the experimental data is better
than the pseudo-first-order model owing to the small RMSE
2
c
and
values. However, both models cannot describe the
ACKNOWLEDGEMENTS
mass transfer of cations onto the material’s surface. The
This research is funded by Vietnam National Foundation
for Science and Technology Development (NAFOSTED)
under grant number 103.02-2018.368.
Table 4. Parameters of nonlinear kinetic models at 303 K.
parameters
COMPETING INTERESTS
Kinetic models
Co (mg/l)
10
The author declares that there is no conflict of interest
Qe (exp) (mg/g)
3.2
regarding the publication of this article.
Qe (cal) (mg/g)
3.11
k1(min-1)
0.1190
0.1185
0.9395
0.0831
3.27
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